WO2012046753A1 - ポリオレフィン系樹脂多孔フィルム - Google Patents

ポリオレフィン系樹脂多孔フィルム Download PDF

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WO2012046753A1
WO2012046753A1 PCT/JP2011/072929 JP2011072929W WO2012046753A1 WO 2012046753 A1 WO2012046753 A1 WO 2012046753A1 JP 2011072929 W JP2011072929 W JP 2011072929W WO 2012046753 A1 WO2012046753 A1 WO 2012046753A1
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porous film
polyolefin resin
resin
group
chemical formula
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PCT/JP2011/072929
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English (en)
French (fr)
Japanese (ja)
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高木義人
牟田隆敏
根本友幸
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三菱樹脂株式会社
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Priority to JP2012537728A priority Critical patent/JP5705868B2/ja
Priority to KR1020137005464A priority patent/KR101514901B1/ko
Priority to CN201180046748XA priority patent/CN103140544A/zh
Priority to US13/877,935 priority patent/US9115277B2/en
Priority to EP11830685.1A priority patent/EP2626380A4/en
Publication of WO2012046753A1 publication Critical patent/WO2012046753A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree

Definitions

  • the present invention relates to a polyolefin-based resin porous film, and can be used as a packaging, sanitary, livestock, agricultural, architectural, medical, separation membrane, light diffusion plate, battery separator, and particularly for a non-aqueous electrolytic battery. It can be suitably used as a separator.
  • Porous polypropylene film with many fine communication holes is used for separation membranes used for the production of ultrapure water, purification of chemicals, water treatment, waterproof and moisture-permeable films used for clothing and sanitary materials, and batteries. It is used in various fields such as battery separators.
  • As a method for producing such a porous polypropylene film there has been known a method in which an inorganic filler such as calcium carbonate and barium sulfate is melt-mixed with polypropylene to form a film and then stretched and made porous.
  • the porous film obtained by this method has a poorly dispersed portion due to the low compatibility of the inorganic filler with polypropylene, and pinholes are likely to occur when stretched and porous. There was a problem that the inorganic filler dropped off and contaminated the process.
  • Patent Document 1 Japanese Patent No. 3443934
  • Patent Document 2 International Publication No. 2002/066233
  • Patent Document 3 describes a method for producing a polypropylene porous film by sequentially biaxially stretching a polypropylene containing acicular ⁇ crystals.
  • a longitudinal stretch ratio (hereinafter referred to as “MD”) is used for the purpose of increasing air holes in the porous film and improving air permeability.
  • MD stretching ratio A method of increasing the stretching ratio
  • TD stretching ratio the transverse stretching ratio
  • Patent Document 3 discloses a resin composition obtained by adding an inorganic substance to a ⁇ -crystal polypropylene resin, and Japanese Patent Application Laid-Open No.
  • Patent Document 1 and Patent Document 2 in order to develop a high porosity and high air permeability, stretching at a higher magnification is required. There was a problem that the shrinkage rate was increased.
  • Patent Document 3 and Patent Document 4 since a large amount of inorganic substances or resin particles are added, pinholes are likely to be generated at the time of stretching and porosity, and during production or use There was a problem that the inorganic material or resin particles dropped off and contaminated the production line. Further, the method described in Patent Document 5 has a problem that not only is it difficult to finely disperse the high melting point resin in polypropylene, but pinholes are easily generated.
  • An object of the present invention is to solve the above problems. That is, an object is to provide a polyolefin resin porous film having high air permeability and high porosity.
  • the present invention provides a polyolefin resin porous film composed of a resin composition (a) comprising a polyolefin resin as a main component and comprising organic-inorganic hybrid particles (f).
  • the addition amount of the organic-inorganic hybrid particles (f) is 1% by mass or more and 10% by mass or less with respect to 100% by mass of the polyolefin resin.
  • the air permeability is preferably 10 seconds / 100 ml or more and 200 seconds / 100 ml or less.
  • At least a layer composed of the resin composition (a) and a layer composed of a resin composition (b) having a crystal melting peak temperature lower than that of the resin composition (a) are laminated. preferable.
  • the present invention provides a separator for a non-aqueous electrolyte secondary battery using the polypropylene resin porous film.
  • the present invention is a porous film having high air permeability characteristics and high porosity, and has excellent characteristics such as breakdown characteristics when used as a separator for a non-aqueous electrolyte secondary battery.
  • the polyolefin resin porous film can be provided.
  • the expression “main component” includes the intention to allow other components to be contained within a range that does not interfere with the function of the main component, unless otherwise specified.
  • the content ratio of the components is not specified, but the main component includes 50% by mass or more, preferably 70% by mass or more, particularly preferably 90% by mass or more (including 100%) in the composition. It is.
  • “X to Y” (X and Y are arbitrary numbers) is described, it means “preferably greater than X” and “preferably smaller than Y” with the meaning of “X to Y” unless otherwise specified. Is included.
  • Polyolefin resin porous film examples of the polyolefin resin used in the polyolefin resin porous film include homopolymers or copolymers obtained by polymerizing ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexane and the like. Among these, a polypropylene resin and a polyethylene resin are preferable.
  • Polypropylene resins include homopropylene (propylene homopolymer), or propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. Random copolymers or block copolymers with ⁇ -olefins may be mentioned. Among these, homopolypropylene is more preferably used from the viewpoint of maintaining the mechanical strength and heat resistance of the laminated porous film.
  • the polypropylene resin preferably has an isotactic pentad fraction (mmmm fraction) exhibiting stereoregularity of 80 to 99%. More preferably 83 to 98%, and still more preferably 85 to 97%. If the isotactic pentad fraction is too low, the mechanical strength of the film may be reduced.
  • the upper limit of the isotactic pentad fraction is defined by the upper limit that can be obtained industrially at the present time, but this is not the case when a more regular resin is developed in the industrial level in the future. is not.
  • the isotactic pentad fraction (mmmm fraction) is the same direction for all five methyl groups that are side chains with respect to the main chain of carbon-carbon bonds composed of any five consecutive propylene units. Means the three-dimensional structure located at or its proportion. Signal assignment of the methyl group region is as follows. It conformed to Zambelli et al (Macromolecules 8,687, (1975)).
  • Mw / Mn which is a parameter indicating a molecular weight distribution
  • Mw / Mn is 2.0 to 10.0. More preferred is 2.0 to 8.0, and still more preferred is 2.0 to 6.0. This means that the smaller the Mw / Mn is, the narrower the molecular weight distribution is.
  • Mw / Mn is less than 2.0, problems such as a decrease in extrusion moldability occur, and it is difficult to produce industrially.
  • Mw / Mn exceeds 10.0, low molecular weight components increase, and the mechanical strength of the laminated porous film tends to decrease.
  • Mw / Mn is obtained by GPC (gel permeation chromatography) method.
  • the melt flow rate (MFR) of the polypropylene resin is not particularly limited, but usually the MFR is preferably 0.5 to 15 g / 10 minutes, and 1.0 to 10 g / 10 minutes. It is more preferable. When the MFR is 0.5 g / 10 min or more, the resin has a high melt viscosity at the time of molding, and sufficient productivity can be ensured. On the other hand, the mechanical strength of the obtained polyolefin resin porous film can be sufficiently maintained by setting it to 15 g / 10 min or less. MFR is measured according to JIS K7210 under conditions of a temperature of 230 ° C. and a load of 2.16 kg.
  • polypropylene resin examples include trade names “Novatech PP” “WINTEC” (manufactured by Nippon Polypro), “Notio” “Toughmer XR” (manufactured by Mitsui Chemicals), “Zeras” “Thermolan” (manufactured by Mitsubishi Chemical) , “Sumitomo Noblen”, “Tough Selenium” (manufactured by Sumitomo Chemical Co., Ltd.), “Prime TPO” (manufactured by Prime Polymer Co., Ltd.), “Adflex”, “Adsyl”, “HMS-PP (PF814)” (manufactured by Sun Allomer Co., Ltd.), “Versify” ",” Inspire “(manufactured by Dow Chemical Co., Ltd.), and other commercially available products can be used.
  • the polypropylene resin preferably has ⁇ crystal activity.
  • the ⁇ crystal activity can be regarded as an index indicating that the polypropylene resin produced ⁇ crystals in the film-like material before stretching. If the polypropylene resin in the film-like material before stretching produces ⁇ crystals, micropores can be easily formed by stretching, so that a polyolefin resin porous film having high air permeability can be obtained. Can do.
  • the presence or absence of “ ⁇ crystal activity” is determined when the crystal melting peak temperature derived from the ⁇ crystal is detected by a differential scanning calorimeter described below and / or X-ray described later.
  • a diffraction peak derived from a ⁇ crystal is detected by measurement using a diffractometer, it is determined to have “ ⁇ crystal activity”.
  • the polyolefin-based resin porous film is heated at a heating rate of 10 ° C./min from 25 ° C. to 240 ° C. for 1 minute by a differential scanning calorimeter, and then cooled at a cooling rate of 10 ° C. from 240 ° C. to 25 ° C.
  • the crystal melting peak temperature (Tm ⁇ ) derived from the ⁇ crystal of the polypropylene resin is detected. If it is, it is determined that it has ⁇ crystal activity.
  • the ⁇ crystal activity of the polyolefin resin porous film is calculated by the following formula using the crystal heat of fusion derived from the ⁇ crystal of the polypropylene resin ( ⁇ Hm ⁇ ) and the crystal heat of heat derived from the ⁇ crystal ( ⁇ Hm ⁇ ). is doing.
  • ⁇ crystal activity (%) [ ⁇ Hm ⁇ / ( ⁇ Hm ⁇ + ⁇ Hm ⁇ )] ⁇ 100
  • the amount of heat of crystal melting derived from the ⁇ crystal ( ⁇ Hm ⁇ ) detected mainly in the range of 145 ° C. or higher and lower than 160 ° C., and mainly detected at 160 ° C. or higher and 170 ° C. or lower.
  • the amount of heat of crystal melting ( ⁇ Hm ⁇ ) derived from the ⁇ crystal detected mainly in the range of 120 ° C. or more and less than 140 ° C. It can be calculated from the crystal melting calorie ( ⁇ Hm ⁇ ) derived from the ⁇ crystal detected in the range of from 0 ° C. to 165 ° C.
  • the polyolefin resin porous film preferably has a high ⁇ crystal activity, and the ⁇ crystal activity is preferably 20% or more. More preferably, it is 40% or more, and particularly preferably 60% or more. If the polyolefin-based resin porous film has a ⁇ -crystal activity of 20% or more, it indicates that a large amount of ⁇ -crystals of polypropylene-based resin can be produced even in a film-like material before stretching, and it is fine and uniform by stretching. As a result, a separator for a lithium ion lithium battery having high mechanical strength and excellent air permeability can be obtained.
  • the upper limit value of the ⁇ crystal activity is not particularly limited, but the higher the ⁇ crystal activity, the more effective the effect is obtained, so the closer it is to 100%, the better.
  • the ⁇ crystal activity is the state of the entire polyolefin resin porous film even in the case where the polyolefin resin porous film of the present invention has a single-layer structure or when other porous layers are laminated. Can be measured.
  • ⁇ crystal nucleating agent examples include those shown below, but are not particularly limited as long as they increase the formation and growth of ⁇ crystals of polypropylene resin, and two or more types are mixed. May be used.
  • examples of the ⁇ crystal nucleating agent include amide compounds; tetraoxaspiro compounds; quinacridones; iron oxides having a nanoscale size; potassium 1,2-hydroxystearate, magnesium benzoate or magnesium succinate, magnesium phthalate, etc.
  • Alkali or alkaline earth metal salts of carboxylic acids represented by: aromatic sulfonic acid compounds represented by sodium benzenesulfonate or sodium naphthalenesulfonate; diesters or triesters of dibasic or tribasic carboxylic acids; phthalocyanines Phthalocyanine pigments typified by blue, etc .; two-component compounds comprising component A which is an organic dibasic acid and component B which is an oxide, hydroxide or salt of a Group IIA metal in the periodic table; cyclic phosphorus compounds And magnesium compound Such composition comprising the like.
  • specific types of nucleating agents are described in JP-A No. 2003-306585, JP-A No. 06-289656, and JP-A No. 09-194650.
  • ⁇ crystal nucleating agent Commercially available products of ⁇ crystal nucleating agent are ⁇ crystal nucleating agent “NJESTER NU-100” manufactured by Shin Nippon Rika Co., Ltd.
  • Specific examples of polypropylene resins to which ⁇ crystal nucleating agent is added include polypropylene “Bepol® B” manufactured by Aristech. -022SP ”, polypropylene manufactured by Borealis“ Beta ( ⁇ ) -PP BE60-7032 ”, polypropylene manufactured by Mayzo“ BNX BETAPP-LN ”, and the like.
  • Organic inorganic hybrid particles (f) In the present invention, it is important that the organic-inorganic hybrid particles (f) comprise.
  • the organic / inorganic hybrid particle (f) is a composite particle in which an organic polymer and an inorganic material are uniformly distributed in the same particle.
  • the characteristics and flexibility of the inorganic material such as wear resistance and heat resistance It is a particle having both characteristics as an organic polymer. Since the particles (f) are contained, since the affinity with the polyolefin resin is high, the adhesion with the polyolefin resin is also good, and at the interface between the polyolefin resin and the particles (f). Delamination hardly occurs.
  • organic-inorganic hybrid particles (f) examples include organic silicone fine particles.
  • the organic silicone fine particles are composed of a polysiloxane crosslinked structure.
  • This polysiloxane crosslinked structure is a structure in which siloxane units form a three-dimensional network structure.
  • the present invention does not particularly limit the type and ratio of the siloxane units constituting the polysiloxane crosslinked structure.
  • Examples of the polysiloxane crosslinked structure include siloxane units represented by the following chemical formula 1 and siloxane represented by the chemical formula 2 Unit, a siloxane unit represented by the chemical formula 3, a siloxane unit represented by the chemical formula 4, a siloxane unit represented by the chemical formula 5 and a siloxane unit represented by the chemical formula 6, and the following conditions 1 to 3: Those satisfying at the same time are preferred.
  • R 1 , R 3 non-reactive hydrocarbon group
  • R 2 , R 4 organic group having a reactive group selected from the following reactive group group reactive group group: acryloxy group, methacryloxy group, vinyl group and mercapto group
  • the siloxane unit represented by Chemical Formula 1 is a silicic anhydride unit. Further, the siloxane unit represented by Chemical Formula 2 is a hydroxysiloxane unit.
  • R 1 in Chemical formula 3 is a non-reactive hydrocarbon group.
  • a non-reactive hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an aralkyl group, and the like.
  • a C 1 -C such as a methyl group, an ethyl group, a propyl group, etc. 3 alkyl groups are preferred, and methyl groups are more preferred.
  • Examples of the siloxane unit represented by Chemical Formula 3 include a methylsiloxane unit, an ethylsiloxane unit, and a propylsiloxane unit, with a methylsiloxane unit being preferred.
  • R 2 in Chemical formula 4 is an organic group having a specific reactive group.
  • the specific reactive group include acryloxy group, methacryloxy group, vinyl group, and mercapto group.
  • the organic group having such a reactive group are 1) an organic group having an acryloxy group such as 2-acryloxyethyl group, 3-acryloxypropyl group, etc., 2) 2-methacryloxyethyl group, 3-methacryloxypropyl group
  • An organic group having a methacryloxy group such as 3) an organic group having a vinyl group such as a vinyl group, an allyl group, an isopropenyl group, or a 2-methylallyl group, and 4) an organic group having a mercapto group, such as a mercaptopropyl group or a mercaptoethyl group.
  • the siloxane units represented by Chemical Formula 4 are: 1) siloxane units having an acryloxy group such as 2-acryloxyethylsiloxane units and 3-acryloxypropylsiloxane units, 2) 2-methacryloxyethylsiloxane units, 3-methacryloxy Siloxane units having a methacryloxy group such as propylsiloxane units, 3) siloxane units having a vinyl group such as vinylsiloxane units, allylsiloxane units, isopropenylsiloxane units, and 4) mercapto groups such as mercaptopropylsiloxane units and mercaptoethylsiloxane units.
  • siloxane units having an acryloxy group and siloxane units having a methacryloxy group are preferable.
  • R 3 in Chemical formula 5 is the same as described above for R 1 in Chemical formula 3 .
  • R 4 in Chemical formula 6 is the same as described above for R 2 in Chemical formula 4 .
  • Hydroxy siloxane units having inter alia acryloxy group, hydroxy siloxane unit preferably has a methacryloxy group.
  • the organosilicone fine particles of the present invention are composed of the polysiloxane crosslinked structure as described above, and have a circular ring shape as a whole, with an average outer diameter of 0.05 to 15 ⁇ m and an average inner diameter. Is 0.01 to 10 ⁇ m, and the difference between the average value of the outer diameter and the average value of the inner diameter is in the range of 0.04 to 5 ⁇ m, but the average value of the outer diameter is 0.1 to 8 ⁇ m. Are preferably in the range of 0.05 to 6 ⁇ m, and the difference between the average value of the outer diameter and the average value of the inner diameter is in the range of 0.5 to 3 ⁇ m.
  • both the average value of the outer diameter and the average value of the inner diameter are obtained by subjecting the organosilicone fine particles of the present invention to a scanning electron microscope and extracting 100 of the arbitrary 100 extracted from the secondary electron image. It is the value which measured the diameter and the internal diameter, respectively, and calculated
  • the method for producing the organosilicone fine particles of the present invention is a method for producing the aforementioned organosilicone fine particles of the present invention, which is a silanol group-forming silicon compound represented by the following chemical formula 7, and a silanol group-forming property represented by the chemical formula 8:
  • the silanol group-forming silicon compound represented by Chemical Formula 7 is a compound that results in the formation of the siloxane unit represented by Chemical Formula 1 and the siloxane unit represented by Chemical Formula 2.
  • X in Chemical Formula 7 is 1) an alkoxyethoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, and 2) an alkoxyethoxy group having 1 to 4 carbon atoms such as a methoxyethoxy group or a butoxyethoxy group.
  • an acyloxy group having 2 to 4 carbon atoms such as an acetoxy group or a propioxy group
  • an N, N-dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as a dimethylamino group or a diethylamino group
  • a hydroxyl group such as a hydroxyl group
  • a halogen atom such as a chlorine atom or a bromine atom
  • 7) a hydrogen atom a hydrogen atom.
  • Examples of the silanol group-forming silicon compound represented by Chemical Formula 7 include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, trimethoxyethoxysilane, tributoxyethoxysilane, tetraacetoxysilane, tetrapropoxysilane, tetraacetoxysilane, tetra (Dimethylamino) silane, tetra (diethylamino) silane, silanetetraol, chlorosilanetriol, dichlorodisianol, tetrachlorosilane, chlorotrihydrogensilane, and the like, among others, tetramethoxysilane, tetraethoxysilane, tetra Butoxysilane and tetrapropoxysilane are preferred.
  • the silanol group-forming silicon compound represented by Chemical formula 8 is a compound that results in the formation of the siloxane unit represented by Chemical formula 3 and the siloxane unit represented by Chemical formula 5.
  • R 5 in Chemical formula 8 is the same as described above for R 1 in Chemical formula 3
  • Y in Chemical formula 8 is the same as described above for X in Chemical formula 7.
  • Examples of the silanol group-forming silicon compound represented by Chemical Formula 8 include methyltrimethoxysilane, ethyltriethoxysilane, propyltributoxysilane, butyltributoxysilane, phenyltrimethoxyethoxysilane, methyltributoxysilane, methyltriacetoxysilane, Examples include methyltripropoxysilane, methyltriacetoxysilane, methyltri (dimethylamino) silane, methyltri (diethylamino) silane, methylsilanetriol, methylchlorodisianol, methyltrichlorosilane, and methyltrihydrogensilane.
  • the average particle size of the organic-inorganic hybrid particles (f) is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and the upper limit is preferably 10.0 ⁇ m or less, more preferably 5.0 ⁇ m or less.
  • An average particle size of 0.01 ⁇ m or more is preferable from the viewpoint of dispersibility of the organic-inorganic hybrid particles (f).
  • the average particle diameter is 10.0 ⁇ m or more, the pore diameter becomes too large when stretched, which is not preferable from the viewpoint of becoming a pinhole or reducing the mechanical strength.
  • the “average particle diameter” is a value measured according to a method using SEM.
  • the amount of the organic-inorganic hybrid particles (f) added to the polyolefin resin is preferably 10% by mass or less with respect to 100% by mass of the polyolefin resin.
  • the addition amount of the organic-inorganic hybrid particles (f) 10% by mass or less, the mechanical strength of the polyolefin-based resin porous film can be sufficiently secured, and the porous film is sufficiently contaminated by dropping of the particles. It is preferable because it can be suppressed.
  • the lower limit of the addition amount of the organic-inorganic hybrid particles (f) is not particularly limited, but is preferably 1% by mass or more, and more preferably 3% by mass or more. If the addition amount of the organic-inorganic hybrid particles (f) is 1% by mass or more, it is preferable because high air permeability characteristics can be sufficiently obtained as compared with the case where the organic-inorganic hybrid particles (f) are not added.
  • additives generally added to the resin composition can be added as appropriate within a range that does not significantly impair the effects of the present invention.
  • the additive include recycling resin, silica, talc, kaolin, calcium carbonate, and the like, which are added for the purpose of improving and adjusting molding processability, productivity, and various physical properties of the laminated porous film.
  • Inorganic particles such as, pigments such as titanium oxide and carbon black, flame retardants, weathering stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents, Examples thereof include additives such as antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, and coloring agents.
  • additives such as antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, and coloring agents.
  • a low molecular weight compound from the viewpoint of air permeability characteristics.
  • the low molecular weight compound include low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polystyrene, alicyclic saturated hydrocarbon resin, wax, and modified products thereof.
  • These low molecular compounds can be selected as appropriate compounds by selecting the polyolefin resin of the present invention.
  • the polyolefin resin is a polypropylene resin
  • the low molecular weight compound is preferably a low molecular weight polypropylene.
  • one or more of these low molecular weight compounds may be contained.
  • the layer (A layer) which consists of the resin composition (a) which has the said polyolefin resin as a main component, and the layer (b) which consists of a resin composition (b) whose crystal melting peak temperature is lower than the said resin composition (a) ( B layer) is preferably laminated, and as the resin composition (a), a layer made of a resin composition containing a polypropylene resin as a main component, and as the resin composition (b), a polyethylene resin It is more preferable that a layer composed of a resin composition containing as a main component is laminated.
  • shutdown characteristics By laminating the layer composed of the resin composition (b), shutdown characteristics (SD characteristics) can be imparted when used as a separator for a non-aqueous electrolyte secondary battery.
  • Specific examples include a two-layer structure in which A layers / B layers are stacked, a three-layer structure in which A layers / B layers / A layers, or B layers / A layers / B layers are stacked.
  • the physical properties of the polyolefin resin porous film of the present invention can be freely adjusted by the layer constitution, lamination ratio, composition of each layer, and production method.
  • the density of the polyethylene resin is preferably 0.910 to 0.970 g / cm 3 , more preferably 0.930 to 0.970 g / cm 3 , and 0.940 to 0.970 g / cm 3. 3 is more preferable.
  • a density of 0.910 g / cm 3 or more is preferable because it can have appropriate SD characteristics.
  • it is 0.970 g / cm 3 or less, it can have an appropriate SD characteristic and is preferable in that the stretchability is maintained.
  • the density is measured according to JIS K7112 using the density gradient tube method. can do.
  • the melt flow rate (MFR) of the polyethylene resin is not particularly limited, but usually the MFR is preferably 0.03 to 30 g / 10 minutes, and preferably 0.3 to 10 g / 10 minutes. It is more preferable. If the MFR is 0.03 g / 10 min or more, the melt viscosity of the resin during the molding process is sufficiently low, which is excellent in productivity and preferable. On the other hand, if it is 30 g / 10 minutes or less, since sufficient mechanical strength can be obtained, it is preferable. MFR is measured in accordance with JIS K7210 under conditions of a temperature of 190 ° C. and a load of 2.16 kg.
  • the polymerization catalyst for the polyethylene resin is not particularly limited, and may be any one such as a Ziegler type catalyst, a Philips type catalyst, or a Kaminsky type catalyst.
  • a polymerization method of the polyethylene resin there are a one-stage polymerization, a two-stage polymerization, or a multistage polymerization more than that, and any method of the polyethylene resin can be used.
  • the porosity promoting compound X is not limited, but specific examples thereof include a porosity promoting compound X selected from a modified polyolefin resin, an alicyclic saturated hydrocarbon resin or a modified product thereof, an ethylene copolymer, or a wax. It is more preferable that at least one of them is included. Among these, an alicyclic saturated hydrocarbon resin or a modified product thereof, an ethylene copolymer, or a wax, which is more effective when made porous, is more preferable, and a wax is more preferable from the viewpoint of moldability.
  • Examples of alicyclic saturated hydrocarbon resins and modified products thereof include petroleum resins, rosin resins, terpene resins, coumarone resins, indene resins, coumarone-indene resins, and modified products thereof.
  • Examples of petroleum resins include aliphatic petroleum resins mainly containing C5 fraction, aromatic petroleum resins mainly containing C9 fraction, copolymer petroleum resins thereof, and alicyclic petroleum resins.
  • Examples of the terpene resin include terpene resins and terpene-phenol resins from ⁇ -pinene
  • examples of the rosin resin include rosin resins such as gum rosin and utudrodin, and esterified rosin resins modified with glycerin and pentaerythritol.
  • the alicyclic saturated hydrocarbon resin and the modified product thereof have relatively good compatibility when mixed with a polyethylene resin, but a petroleum resin is more preferable in terms of color tone and thermal stability, and a hydrogenated petroleum resin is used. More preferably.
  • Hydrogenated petroleum resin is obtained by hydrogenating petroleum resin by a conventional method.
  • Examples thereof include hydrogenated aliphatic petroleum resins, hydrogenated aromatic petroleum resins, hydrogenated copolymer petroleum resins and hydrogenated alicyclic petroleum resins, and hydrogenated terpene resins.
  • hydrogenated petroleum resins hydrogenated alicyclic petroleum resins obtained by copolymerizing and hydrogenating a cyclopentadiene compound and an aromatic vinyl compound are particularly preferable.
  • Examples of commercially available hydrogenated petroleum resins include “ALCON” (manufactured by Arakawa Chemical Industries).
  • the ethylene copolymer in the present invention is a compound obtained by copolymerizing ethylene and one or more of vinyl acetate, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or carboxylic acid ester. It is.
  • the ethylene copolymer preferably has an ethylene monomer unit content of 50% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more.
  • the content of ethylene monomer units is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. If the content of the ethylene monomer unit is within a predetermined range, a porous structure can be formed more efficiently.
  • ethylene copolymer those having an MFR (JIS K7210, temperature: 190 ° C., load: 2.16 kg) of 0.1 g / 10 min to 10 g / 10 min are preferably used.
  • MFR JIS K7210, temperature: 190 ° C., load: 2.16 kg
  • the MFR is 0.1 g / 10 min or more, the extrudability can be maintained satisfactorily.
  • the MFR is 10 g / 10 min or less, the strength of the film is hardly lowered, which is preferable.
  • the ethylene-based copolymers are “EVAFLEX” (Mitsui / DuPont Polychemical Co., Ltd.), “Novatech EVA” (Nippon Polyethylene Co., Ltd.) as an ethylene-vinyl acetate copolymer, and “NUC” as an ethylene-acrylic acid copolymer.
  • the wax in the present invention is an organic compound that satisfies the following properties (a) and (b).
  • the melting point is 40 ° C to 200 ° C.
  • the melt viscosity at a temperature 10 ° C. higher than the melting point is 50 Pa ⁇ s or less.
  • ⁇ For wax including polar or nonpolar wax, polypropylene wax, polyethylene wax and wax modifier.
  • paraffin wax, polypropylene wax, polyethylene wax, and microcrystalline wax are preferable because a porous structure can be efficiently formed.
  • Commercially available polypropylene waxes include “Mitsui High Wax” (manufactured by Mitsui Chemicals), “Biscol” (manufactured by Sanyo Chemical Industries), “Licocene” (manufactured by Clariant Japan), and polyethylene waxes such as “FT- 115 ”(manufactured by Nippon Seiwa Co., Ltd.) and microcrystalline waxes include“ Hi-Mic ”(manufactured by Nippon Seiwa Co., Ltd.).
  • the blending amount of the porosity promoting compound X is set as a lower limit with respect to 100% by mass of the polyethylene resin contained in one layer when the interface between the polyethylene resin and the porosity promoting compound X is peeled to form micropores. 1 mass% or more is preferable, 5 mass% or more is more preferable, and 10 mass% or more is still more preferable.
  • the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
  • thermoplastic resin may be used as long as the thermal characteristics of the porous film, specifically, the porosity is not impaired.
  • thermoplastic resins include styrene resins such as styrene, AS resin, and ABS resin: polyvinyl chloride, fluorine resin, polyethylene terephthalate, polybutylene terephthalate, and polycarbonate.
  • ester resins such as polyarylate
  • Ether resins such as polyacetal, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone or polyphenylene sulfide
  • polyamides such as 6 nylon, 6-6 nylon, 6-12 nylon
  • thermoplastic resins such as resins.
  • thermoplastic elastomer examples include styrene / butadiene, polyolefin, urethane, polyester, polyamide, 1,2-polybutadiene, polyvinyl chloride, and ionomer.
  • additives or other components that are generally blended in the resin composition may be included.
  • the additive include recycling resin, silica, talc, kaolin, carbonic acid, etc., which are added for the purpose of improving / adjusting the processability, productivity, and various physical properties of the laminated porous film.
  • Inorganic particles such as calcium, pigments such as titanium oxide and carbon black, flame retardants, weathering stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents And additives such as antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, and coloring agents.
  • the nucleating agent is preferable because it has an effect of controlling the crystal structure of the polyethylene resin and reducing the porous structure at the time of stretching and opening.
  • the method for producing the non-porous film is not particularly limited, and a known method may be used. For example, a method of melting a thermoplastic resin composition using an extruder, extruding from a T die, and cooling and solidifying with a cast roll. Is mentioned. Moreover, the method of cutting open the film-like thing manufactured by the tubular method and making it planar is also applicable.
  • There are methods for stretching the nonporous film-like material such as a roll stretching method, a rolling method, a tenter stretching method, and a simultaneous biaxial stretching method, and these methods are used alone or in combination of two or more to perform uniaxial stretching or biaxial stretching. . Among these, sequential biaxial stretching is preferable from the viewpoint of controlling the porous structure.
  • the production method is roughly classified into the following four types depending on the order of porous formation and lamination.
  • (I) A method in which each layer is made porous, and then the layers made porous are laminated or bonded with an adhesive or the like.
  • (II) A method of laminating each layer to produce a laminated nonporous film-like material, and then making the nonporous film-like material porous.
  • (III) A method in which one of the layers is made porous and then laminated with another layer of a nonporous film to make it porous.
  • (IV) A method of forming a laminated porous film by preparing a porous layer and then applying a coating such as inorganic / organic particles or depositing metal particles.
  • a coating such as inorganic / organic particles or depositing metal particles.
  • a method of forming a porous layer after preparing is particularly preferable.
  • the pellets are put into an extruder and extruded from a T-die extrusion die to form a film.
  • the type of T die is not particularly limited.
  • the T die may be a multi-manifold type for two types and three layers or a feed block type for two types and three layers.
  • the gap of the T die to be used is determined from the final required film thickness, stretching conditions, draft ratio, various conditions, etc., but is generally about 0.1 to 3.0 mm, preferably 0.5. -1.0 mm. If it is less than 0.1 mm, it is not preferable from the viewpoint of production speed, and if it is more than 3.0 mm, it is not preferable from the viewpoint of production stability because the draft rate increases.
  • the extrusion temperature is appropriately adjusted depending on the flow characteristics and moldability of the resin composition, but is generally preferably 180 to 350 ° C, more preferably 200 to 330 ° C, and further preferably 220 to 300 ° C.
  • a temperature of 180 ° C. or higher is preferable because the viscosity of the molten resin is sufficiently low, the moldability is excellent, and the productivity is improved.
  • the temperature is set to 350 ° C. or lower, it is possible to suppress the deterioration of the resin composition, and hence the mechanical strength of the resulting polyolefin resin porous film.
  • the cooling and solidification temperature by the cast roll is very important in the present invention, and the ratio of the ⁇ crystal of the polyolefin resin in the film can be adjusted.
  • the cooling and solidifying temperature of the cast roll is preferably 80 to 150 ° C, more preferably 90 to 140 ° C, and still more preferably 100 to 130 ° C. It is preferable to set the cooling and solidification temperature to 80 ° C. or higher because the ratio of ⁇ crystals in the film can be sufficiently increased. Moreover, it is preferable to set the temperature to 150 ° C. or lower because troubles such as the extruded molten resin sticking to the cast roll and winding are unlikely to occur, and the film can be efficiently formed into a film.
  • the ⁇ crystal ratio of the polyolefin resin of the film-like material before stretching is adjusted to 30 to 100% by setting the cast roll in the temperature range. More preferably, it is 40 to 100%, more preferably 50 to 100%, and most preferably 60 to 100%.
  • a polyolefin-based resin porous film having good gas permeability can be obtained because it is easily made porous by the subsequent stretching operation.
  • the ⁇ crystal ratio in the film before stretching is detected when the film is heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter.
  • uniaxial stretching may be performed in the longitudinal direction or the transverse direction, or biaxial stretching may be performed.
  • biaxial stretching simultaneous biaxial stretching may be sufficient and sequential biaxial stretching may be sufficient.
  • sequential biaxial stretching is more preferable because the stretching conditions can be selected in each stretching step and the porous structure can be easily controlled.
  • Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching, but the stretching conditions (magnification, temperature) can be easily selected in each stretching step, and the porous structure can be easily controlled. Biaxial stretching is more preferable.
  • the longitudinal direction of the film and the film is referred to as “longitudinal direction”, and the direction perpendicular to the longitudinal direction is referred to as “lateral direction”.
  • stretching in the longitudinal direction is referred to as “longitudinal stretching”
  • stretching in the direction perpendicular to the longitudinal direction is referred to as “lateral stretching”.
  • the stretching temperature needs to be appropriately selected depending on the composition of the resin composition to be used and the crystallization state, but it is preferable to select within the range of the following conditions.
  • the stretching temperature needs to be changed appropriately depending on the composition of the resin composition to be used, the crystal melting peak temperature, the crystallinity, etc., but the stretching temperature in the longitudinal stretching is preferably about 0 to 130 ° C., More preferably, it is controlled in the range of 10 to 120 ° C., more preferably 20 to 110 ° C. Further, it is preferably 2 to 10 times, more preferably 3 to 8 times, still more preferably 4 to 7 times.
  • the stretching temperature in transverse stretching is generally from 100 to 160 ° C., preferably from 110 to 150 ° C., more preferably from 120 to 140 ° C.
  • the preferred longitudinal draw ratio is preferably 1.2 to 10 times, more preferably 1.5 to 8 times, still more preferably 2 to 7 times.
  • the stretching speed in the stretching step is preferably 500 to 12000% / min, more preferably 1500 to 10,000% / min, and further preferably 2500 to 8000% / min.
  • the area ratio is preferably 3 to 48 times, more preferably 5 to 40 times, and still more preferably 10 to 35 times. It is preferable that the area magnification is 3 times or more because sufficient air permeability characteristics can be obtained. Moreover, it is preferable for the area magnification to be 48 times or less because the occurrence of breakage of the porous film during production can be suppressed, and sufficient molding characteristics can be ensured.
  • the polyolefin resin porous film thus obtained is preferably subjected to heat treatment for the purpose of improving dimensional stability.
  • the effect of dimensional stability can be expected by setting the temperature to preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and still more preferably 140 ° C. or higher.
  • the heat treatment temperature is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
  • a heat treatment temperature of 170 ° C. or lower is preferable because the polyolefin resin hardly melts by the heat treatment and the porous structure can be maintained.
  • a relaxation treatment of 1 to 20% may be performed as necessary.
  • a polyolefin resin porous film is obtained by cooling uniformly and winding up.
  • the thickness of the polyolefin resin porous film of the present invention is preferably 5 to 100 ⁇ m. More preferably, it is 8 to 50 ⁇ m, and still more preferably 10 to 30 ⁇ m.
  • the thickness of the polyolefin resin porous film of the present invention is preferably 5 to 100 ⁇ m. More preferably, it is 8 to 50 ⁇ m, and still more preferably 10 to 30 ⁇ m.
  • it is 5 ⁇ m or more, substantially necessary electrical insulation can be obtained. For example, even when a large force is applied to the protruding portion of the electrode, Breaks through the separator for the electrolyte secondary battery and is not easily short-circuited.
  • the electrical resistance of a polyolefin-type resin film can be made small if thickness is 100 micrometers or less, the performance of a battery can fully be ensured.
  • the porosity is preferably 50% or more, and more preferably 55% or more.
  • the porosity is 50% or more, low electrical resistance can be sufficiently secured when used as a separator for a non-aqueous electrolyte secondary battery, and even when used for high output applications, Since energy loss can be suppressed, it is preferable.
  • the upper limit is preferably 90% or less, more preferably 85% or less, and still more preferably 80% or less. If the porosity is 90% or less, the mechanical strength of the polyolefin resin porous film can be sufficiently maintained, and it is also preferable from the viewpoint of secondary processing.
  • the porosity is measured by the method described in the examples.
  • the air permeability of the polyolefin resin porous film of the present invention is preferably 200 seconds / 100 ml or less. If the air permeability is 200 seconds / 100 ml or less, it indicates that the polyolefin-based resin porous film has communication properties, and not only has excellent air permeability properties but also is used as a separator for non-aqueous electrolyte secondary batteries. It is also effective from the viewpoint of output characteristics. On the other hand, the lower limit is not particularly limited, but the air permeability is more preferably 10 seconds / 100 ml or more.
  • the air permeability represents the difficulty of air passing through in the film thickness direction, and is specifically expressed by the number necessary for 100 ml of air to pass through the film. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the easier it is to pass. That is, a smaller value means better communication in the thickness direction of the film, and a larger value means poor communication in the thickness direction of the film. Communication is the degree of connection of holes in the film thickness direction.
  • the air permeability of the polyolefin resin porous film of the present invention is low, it can be used for various applications.
  • a low air permeability means that lithium ions can be easily transferred, which is preferable because battery performance is excellent.
  • the polyolefin resin porous film of the present invention preferably has SD characteristics when used as a separator for a non-aqueous electrolyte secondary battery.
  • the air permeability after heating at 135 ° C. for 5 seconds is preferably 10,000 seconds / 100 ml or more, more preferably 25000 seconds / 100 ml or more, and further preferably 50000 seconds / 100 ml or more.
  • the polyolefin resin porous film of the present invention preferably exhibits breakdown characteristics (BD characteristics) at 160 ° C. or higher. That is, in the polyolefin resin porous film of the present invention, the temperature (breakdown temperature) when the breakdown characteristics are manifested is preferably 160 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 250 ° C. or higher. When the breakdown temperature is less than 160 ° C., there is no difference in the temperature at which the shutdown characteristics and breakdown characteristics are manifested.
  • the polyolefin resin porous film of the present invention is used as a separator for a non-aqueous electrolyte secondary battery. When used, it is not preferable because a battery with sufficient safety cannot be provided.
  • breakdown temperature refers to the lowest temperature among the temperatures at which the polyolefin resin porous film of the present invention breaks when heated by the method described in Examples.
  • the thermal shrinkage rate (TD heat shrinkage rate) in the direction perpendicular to the flow direction of the porous film is preferably less than 10%.
  • the polyolefin-based resin porous film is used as a separator for a non-aqueous electrolyte secondary battery, it is often incorporated into a non-aqueous electrolyte battery in a stacked form of positive electrode / separator / negative electrode / separator.
  • a cylindrical battery generally referred to as 18650 cells is manufactured by winding the stacked units in a band shape.
  • the TD heat shrinkage rate is preferably less than 10%.
  • the thermal contraction rate (MD thermal contraction rate) in the flow direction is also less than 10% in order to prevent the risk of an internal short circuit similarly to the TD thermal contraction rate.
  • a nonaqueous electrolyte secondary battery containing the polyolefin resin porous film of the present invention as a battery separator will be described with reference to FIG.
  • Both electrodes of the positive electrode plate 21 and the negative electrode plate 22 are wound in a spiral shape so as to overlap each other via the battery separator 10, and the outside is stopped with a winding tape to form a wound body.
  • the winding process will be described in detail.
  • One end of the battery separator is passed between the slit portions 1 of the pin, and the pin is slightly rotated to wind one end of the battery separator around the pin. At this time, the surface of the pin is in contact with the heat-resistant layer of the battery separator.
  • the positive electrode and the negative electrode are arranged so as to sandwich the battery separator, and the pins are rotated by a winding machine to wind the positive and negative electrodes and the battery separator. After winding, the pin is pulled out of the wound object.
  • the wound body in which the positive electrode plate 21, the battery separator 10 and the negative electrode plate 22 are integrally wound is accommodated in a bottomed cylindrical battery case and welded to the positive and negative electrode lead bodies 24 and 25.
  • the electrolyte is injected into the battery can, and after the electrolyte has sufficiently penetrated into the battery separator 10 or the like, the positive electrode lid 27 is sealed around the opening periphery of the battery can via the gasket 26, and precharging and aging are performed.
  • a cylindrical non-aqueous electrolyte secondary battery is manufactured.
  • an electrolytic solution in which a lithium salt is used as an electrolytic solution and is dissolved in an organic solvent is used.
  • the organic solvent is not particularly limited.
  • esters such as propylene carbonate, ethylene carbonate, butylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, dimethyl carbonate, methyl propionate or butyl acetate, and nitriles such as acetonitrile.
  • ethers such as tetrahydrofuran, 2-methyltetrahydrofuran or 4-methyl-1,3-dioxolane, or sulfolane.
  • LiPF 6 lithium hexafluorophosphate
  • an alkali metal or a compound containing an alkali metal integrated with a current collecting material such as a stainless steel net is used.
  • the alkali metal include lithium, sodium, and potassium.
  • the compound containing an alkali metal include an alloy of an alkali metal and aluminum, lead, indium, potassium, cadmium, tin or magnesium, a compound of an alkali metal and a carbon material, a low potential alkali metal and a metal oxide, and the like. Or a compound with a sulfide or the like.
  • the carbon material may be any material that can be doped and dedoped with lithium ions, such as graphite, pyrolytic carbons, cokes, glassy carbons, a fired body of an organic polymer compound, Mesocarbon microbeads, carbon fibers, activated carbon and the like can be used.
  • a carbon material having an average particle size of 10 ⁇ m is mixed with a solution in which vinylidene fluoride is dissolved in N-methylpyrrolidone to form a slurry, and this negative electrode mixture slurry is passed through a 70-mesh net. After removing the large particles, uniformly apply to both sides of the negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 ⁇ m and dry, and then compression-molded with a roll press machine, cut, strip-shaped negative electrode plate and We use what we did.
  • lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, manganese dioxide, metal oxide such as vanadium pentoxide or chromium oxide, metal sulfide such as molybdenum disulfide, etc. are used as active materials.
  • These positive electrode active materials are combined with conductive additives and binders such as polytetrafluoroethylene as appropriate, and finished with a current collector material such as a stainless steel mesh as a core material. It is done.
  • a strip-like positive electrode plate produced as follows is used as the positive electrode. That is, lithium graphite oxide (LiCoO 2 ) is added with phosphorous graphite as a conductive additive at a mass ratio of 90: 5 (lithium cobalt oxide: phosphorous graphite) and mixed, and this mixture and polyvinylidene fluoride are mixed with N Mix with a solution in methylpyrrolidone to make a slurry.
  • This positive electrode mixture slurry is passed through a 70-mesh net to remove large particles, and then uniformly applied to both sides of a positive electrode current collector made of an aluminum foil having a thickness of 20 ⁇ m, dried, and then compressed by a roll press. After forming, it is cut into a strip-like positive electrode plate.
  • the longitudinal direction of the polyolefin-based resin porous film is referred to as “longitudinal direction”, and the direction perpendicular to the longitudinal direction is referred to as “lateral direction”.
  • the longitudinal direction of the polyolefin-based resin porous film is referred to as “longitudinal direction”, and the direction perpendicular to the longitudinal direction is referred to as “lateral direction”.
  • Air permeability (Gurley value) The air permeability (second / 100 ml) was measured at room temperature in accordance with JIS P8117. Next, the obtained air permeability value was evaluated as follows. ⁇ : Air permeability is 10 to 200 seconds / 100ml X: Air permeability is less than 10 seconds / 100 ml, or more than 200 seconds / 100 ml
  • Porosity is a numerical value indicating the proportion of the space portion in the polyolefin resin porous film. The porosity is determined by measuring the substantial amount W1 of the polyolefin resin porous film, calculating the mass W0 when the porosity is 0% from the density and thickness of the resin composition, and calculating from these values based on the following formula: did.
  • Porosity Pv (%) ⁇ (W0 ⁇ W1) / W0 ⁇ ⁇ 100 Next, the obtained porosity value was evaluated as follows. ⁇ : Porosity is 55 to 90% X: Porosity is less than 55% or more than 90%
  • the sample in a state constrained to was immersed and heated for 5 seconds. Immediately after heating, it is immersed in a separately prepared cooling bath filled with 25 ° C. glycerin and cooled for 5 minutes, and then washed with 2-propanol (manufactured by Nacalai Tesque, special grade) and acetone (manufactured by Nacalai Tesque, special grade). And dried in an air atmosphere at 25 ° C. for 15 minutes. The air permeability of the sample after drying was measured according to the method (2). Based on the above measurement, the evaluation was made according to the following criteria, and the evaluation of “ ⁇ ” was regarded as having a shutdown characteristic. ⁇ : 50,000 seconds / 100 ml or more ⁇ : 10,000 seconds / 100 ml or more, less than 50000 seconds / 100 ml ⁇ : less than 10,000 seconds / 100 ml
  • the presence or absence of ⁇ -crystal activity was evaluated according to the following criteria depending on whether or not a peak was detected at 145 to 160 ° C., which is the crystal melting peak temperature (Tm ⁇ ) derived from ⁇ -crystal of the polypropylene resin at the time of re-heating. .
  • Tm ⁇ crystal melting peak temperature
  • X When Tm ⁇ is not detected within the range of 145 ° C to 160 ° C (no ⁇ crystal activity) The ⁇ crystal activity was measured with a sample amount of 10 mg in a nitrogen atmosphere.
  • the set temperature was changed to 100 ° C., and the mixture was gradually cooled to 100 ° C. over 10 minutes or more.
  • the display temperature reaches 100 ° C.
  • the sample is taken out and cooled for 5 minutes in an atmosphere of 25 ° C. while being restrained by two aluminum plates.
  • Wide-angle X-ray diffraction measurement was performed on a 40 mm ⁇ circular portion.
  • -Wide-angle X-ray diffraction measurement device manufactured by Mac Science, model number: XMP18A X-ray source: CuK ⁇ ray, output: 40 kV, 200 mA Scanning method: 2 ⁇ / ⁇ scan, 2 ⁇ range: 5 ° to 25 °, scanning interval: 0.05 °, scanning speed: 5 ° / min
  • the presence or absence of ⁇ crystal activity was evaluated as follows from the peak derived from the (300) plane of ⁇ crystal of the polypropylene resin.
  • Example 1 As a ⁇ -crystal nucleating agent, 100% by mass of polypropylene resin (Nippon Polypro, Novatec PP FY6HA, MFR: 2.4 g / 10 min, melting point: 158 ° C.) as a ⁇ crystal nucleating agent is 3,9-bis [4- (N -Cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 0.2% by mass, organic-inorganic hybrid particles (SPT014, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.3 ⁇ m Is added to the same direction twin screw extruder (Toshiba Machine Co., Ltd., caliber: 40 mm ⁇ , L / D: 32), melt kneaded at a set temperature of 300 ° C., and extruded from a strand die. The strands were cooled and solidified in water, and the strands
  • Example 2 A polyolefin resin porous film was produced in the same manner as in Example 1 except that the amount of organic-inorganic hybrid particles (SPT014, Takemoto Yushi Co., Ltd., average particle size: 0.3 ⁇ m) added was 3 mass%. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
  • Example 4 A polyolefin resin porous film was produced in the same manner as in Example 1 except that 1% by mass of organic / inorganic hybrid particles (SPT013, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.6 ⁇ m) was added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
  • Example 5 A polyolefin-based resin porous film was produced in the same manner as in Example 1 except that 5% by mass of organic-inorganic hybrid particles (SPT013, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.6 ⁇ m) were added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
  • Example 1 instead of the organic / inorganic hybrid particles (f), a polyolefin-based polymer was prepared in the same manner as in Example 1 except that 5% by mass of alumina (Sumicorundum AA-07, Sumitomo Chemical Co., Ltd., average particle size: 0.7 ⁇ m) was added. An attempt was made to produce a porous resin film, but an avatar that was thought to be caused by poor dispersibility of alumina during extrusion from a T-die was generated, so that a good nonporous film-like product could not be obtained.
  • alumina Sudicorundum AA-07, Sumitomo Chemical Co., Ltd., average particle size: 0.7 ⁇ m
  • Example 2 A polyolefin-based resin porous film was produced in the same manner as in Example 1 except that 3% by mass of polymethylpentene (TPX RT-18, manufactured by Mitsui Chemicals, Inc.) was added instead of the organic / inorganic hybrid particles (f). The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
  • TPX RT-18 polymethylpentene
  • Example 3 A polyolefin-based resin porous film was produced in the same manner as in Example 1 except that 3% by mass of polycarbonate (Taflon A1900, manufactured by Idemitsu Kosan Co., Ltd.) was added instead of the organic-inorganic hybrid particles (f). The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
  • Example 4 A polyolefin resin porous film was produced in the same manner as in Example 1 except that the organic-inorganic hybrid particles (f) were not added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 1.
  • Example 6 As the A layer, a polypropylene resin (Novatech PP FY6HA, MFR: 2.4 g / 10 min, melting point: 158 ° C.) 100% by mass with respect to 100% by mass as a ⁇ -nucleating agent, 3,9-bis [ 0.2% by mass of 4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, organic-inorganic hybrid particles (SPT014, Takemoto Yushi Co., Ltd., average particle size : 0.3 ⁇ m) is added to 3% by mass, then charged into the same-direction twin screw extruder (manufactured by Toshiba Machine Co., Ltd., caliber: 40 mm ⁇ , L / D: 32), melt-kneaded at a set temperature of 300 ° C., and a strand die After further extrusion, the strand was cooled and solidified in water, and the strand was
  • high-density polyethylene manufactured by Prime Polymer Co., Ltd., Hi-Zex 3600F, MFR: 1.0 g / 10 min, melting point: 133 ° C.
  • resin composition constituting the B layer.
  • Example 7 A polyolefin-based resin porous film was produced in the same manner as in Example 6 except that the amount of organic / inorganic hybrid particles (SPT014, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.3 ⁇ m) was changed to 5% by mass for layer A. did. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 2.
  • Example 5 For layer A, the same as in Example 6 except that 5% by mass of alumina (Sumicorundum AA-03, manufactured by Sumitomo Chemical Co., Ltd., average particle size: 0.3 ⁇ m) was added instead of the organic-inorganic hybrid particles (f).
  • alumina Sudicorundum AA-03, manufactured by Sumitomo Chemical Co., Ltd., average particle size: 0.3 ⁇ m
  • Example 6 A polyolefin resin porous film was produced in the same manner as in Example 6 except that the organic-inorganic hybrid particles (f) were not added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 2.
  • Example 8 As a ⁇ -crystal nucleating agent, 100% by mass of polypropylene resin (Nippon Polypro, Novatec PP FY6HA, MFR: 2.4 g / 10 min, melting point: 158 ° C.) as a ⁇ crystal nucleating agent is 3,9-bis [4- (N -Cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 0.2% by mass, organic-inorganic hybrid particles (SPT014, manufactured by Takemoto Yushi Co., Ltd., average particle size: 0.3 ⁇ m ) Is added to the same direction twin screw extruder (Toshiba Machine Co., Ltd., caliber: 40 mm ⁇ , L / D: 32), melt kneaded at a set temperature of 300 ° C., and extruded from a strand die. The strands were cooled and solidified in water, and the strands were
  • the polypropylene resin composition was extruded from a T-die and cooled and solidified with a casting roll at 127 ° C. to prepare a nonporous film-like material.
  • the non-porous film-like material was stretched 4.6 times in the longitudinal direction using a longitudinal stretching machine, stretched 3 times in the lateral direction at 150 ° C. by a lateral stretching machine, and then subjected to heat setting / relaxation treatment.
  • the resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
  • Example 9 A polyolefin-based resin porous film was produced in the same manner as in Example 8, except that the nonporous membrane was stretched four times in the transverse direction at 150 ° C. by a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
  • Example 10 A polyolefin-based resin porous film was produced in the same manner as in Example 8, except that the nonporous membrane was stretched 5 times in the transverse direction at 150 ° C. by a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
  • Example 12 A polyolefin-based resin porous film was produced in the same manner as in Example 8, except that the nonporous membrane was stretched 7 times in the transverse direction at 150 ° C. by a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
  • Example 5 A polyolefin resin porous film was produced in the same manner as in Example 8 except that the organic-inorganic hybrid particles (f) were not added. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
  • Comparative Example 6 A polyolefin-based resin porous film was produced in the same manner as in Comparative Example 5 except that the nonporous membrane was stretched 5 times in the transverse direction at 150 ° C. by a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
  • Comparative Example 7 A polyolefin-based resin porous film was produced in the same manner as in Comparative Example 5, except that the nonporous membrane was stretched 6 times in the transverse direction at 150 ° C. with a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
  • Comparative Example 8 A polyolefin-based resin porous film was produced in the same manner as in Comparative Example 5 except that the nonporous membrane was stretched 7 times in the transverse direction at 150 ° C. with a transverse stretching machine. The resulting polyolefin resin porous film was evaluated for physical properties, and the results are summarized in Table 3.
  • the polyolefin resin porous film obtained in any of the examples had high air permeability and a high porosity.
  • inorganic particles such as alumina are added instead of the organic-inorganic hybrid particles (f)
  • the polyolefin resin porous film to which the organic-inorganic hybrid particles (f) were added was able to obtain even higher transmission characteristics when the area magnification was increased.
  • the organic-inorganic hybrid particles (f) were not added as in Comparative Examples 5 to 8, the air permeability characteristics were deteriorated by increasing the area magnification.
  • the polyolefin resin porous film of the present invention can be applied to various uses that require air permeability.

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